CN102449791A - Thermoelectric module with insulated substrate - Google Patents
Thermoelectric module with insulated substrate Download PDFInfo
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- CN102449791A CN102449791A CN2010800237638A CN201080023763A CN102449791A CN 102449791 A CN102449791 A CN 102449791A CN 2010800237638 A CN2010800237638 A CN 2010800237638A CN 201080023763 A CN201080023763 A CN 201080023763A CN 102449791 A CN102449791 A CN 102449791A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom
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Abstract
In a thermoelectric module comprising a series of p and n type semiconductors con not nected in series by conductive contacts, the conductive contacts are in contact with a substrate of moderate to high thermal conductivity that is electrically insulated from the conductive contacts by a resistive surface layer comprising a ceramic material.
Description
Technical field
The present invention relates to comprise a series of p that are connected in series through conductive contact and electrothermal module of n N-type semiconductor N and preparation method thereof, wherein said electrothermal module is supported on the substrate with certain electric insulation.
Background technology
Thermoelectric generator and Peltier structure itself disclose a period of time.One side heated and p that opposite side is cooled and n type doped semiconductor transmission charge through external circuit, and can make electric work through the load in the circuit.The heat that in this method, realizes receives the Carnot efficiency limitations, among others to the conversion efficiency of electric energy in moving of heat.Therefore, be that 1000K, " low temperature " side temperature are the efficient that can obtain (1000-400): 1000=60% under the situation of 400K in the high temperature side temperature.Yet, the highlyest up to now can only obtain 10% efficient.
On the other hand, when when this structure applies direct current, heat transfers to opposite side from a side.This Peltier structure is worked as heat pump, therefore is suitable for cooling device parts, vehicle or building.Than routine heating, based on the heating of Peltier principle also more preferably, because than corresponding to the energy equivalence that provides, it transmits more heats.
Cronin B.Vining for example, ITS Short Course on Thermoelectricity, (on November 8th, 1993, Yokohama, Japan) has looked back effect and material well.
At present, thermoelectric generator be used in the negative electrode that is used in the aviation detector for example to produce direct current, be used for pipeline anticorrosive, be used for energy being provided and being used to make broadcast receiver and television operations to lighted buoy and radio-beacon buoy.The advantage of thermoelectric generator is that it is extremely reliable.For example, they can be in any atmospheric conditions (such as atmospheric humidity) work down; There is not the mass transfer that is easy to produce fault, and has only electric charge to shift.Can use from hydrogen to the natural gas, any fuel of gasoline, kerosene, diesel fuel, the fuel (for example rapeseed methylester) that obtains until biological mode.
Therefore thermoelectric energy conversion can adapt to tomorrow requirement very neatly, generates such as hydrogen economy or the energy that is derived from regenerative resource.
An attractive especially application is to be used for converting (discarding) heat to electric energy in motor vehicle, heating system or power station.The heat energy that utilizes at present even can be partially recycled at least through thermoelectric generator, but the efficient of prior art far below 10%, so quite a few energy does not still obtain utilizing.Therefore in the utilization of waste heat, also exist and obtain more high efficiency actuating force.
It also is very attractive directly solar energy converting being become electric energy.The concentrator such such as parabola shaped recess can focus on solar energy in the thermoelectric generator that produces electric energy.
Yet, as heat pump the time, also need higher efficient.
Assessed according to its efficient for thermoelectric active material based.Thermoelectric material is known as Z factor (quality factor) in the characteristic on aspect this:
Wherein S is a Seebeck coefficient, and σ is a conductivity, and κ is a thermal conductivity.Preferred thermal conductivity is very low, conductivity is very high, the very large thermoelectric material of Seebeck coefficient, so that quality factor obtain maximum.
Product S
2σ is known as power factor, and is used for the comparison of thermoelectric material.
In addition, usually report also that nondimensional product ZT is to be used for the comparison purpose.At present known thermoelectric material has under optimum temperature and is about 1 maximum ZT value.Exceeding under the situation of this optimum temperature, the ZT value is significantly less than 1 usually.
More accurate analysis shows can be according to following formula computational efficiency (simultaneously referring to Mat.Sci.and Eng.B29 (1995) 228):
Wherein,
Therefore, aim to provide a kind of thermoelectric material with maximum Z value and high realized temperature difference.From the solid state physics angle, also have a lot of problems to overcome:
High σ value requires the electron mobility in the material high, that is, electronics (the perhaps hole in the p type electric conducting material) can not be fettered by atomic nucleus strongly.Material with high conductivity σ also has high thermal conductivity (Wiedemann-Franz law) usually, and this makes can not advantageously influence Z.The material that adopts at present is (such as Bi
2Te
3) formed compromise.For example, make the decline degree of decline degree specific heat conductance of conductivity low through alloying.Therefore preferred alloy, the for example (Bi of using
2Te
3)
90(Sb
2Te
3)
5(Sb
2Se
3)
5Or Bi
12Sb
23Te
65
For high efficiency thermoelectric materials, the preferred also necessary boundary condition that satisfies further.For example, they must be enough thermally-stabilised so that can under service conditions, work for many years, and significantly sacrificing does not appear in efficient simultaneously.This requires self at high temperature heat-staple phase, stable phase composition, and alloying component can be ignored to the diffusion of the contact material of adjacency.
In the production process of electrothermal module, need n type and p type conductor all the time.For reaching the maximal efficiency of module, promptly in the Peltier structure, reach maximum cooling performance or in the Seebeck structure, reach maximum generation machine performance, p type and n type electric conducting material also must match each other as much as possible.This is specifically related to Seebeck coefficient (S (n)=-S (p)) ideally, conductivity (σ (n)=σ (p) ideally), thermal conductivity (λ (n)=λ (p) ideally) and thermal coefficient of expansion parameters such as (α (n)=α (p) ideally).
In electrothermal module, the metal/semiconductor material connects together through electrode (being used to transmit the electric current of generation), and with other external component electric insulation.Electrode contact electrical insulator material, said insulating material allows heat to flow to thermoelectric material well from thermal source.Therefore need thin layer of insulator material, and must form the contact good interface.
Usually, electrothermal module has for example by SiO
2, Al
2O
3Or the ceramic wafer processed of AlN is as the strutting piece with electrical insulating property, and the voltage that is produced to prevent is short-circuited.In order between thermal source and thermoelectric material, to form good heat flow, key is that substrate has good thermal conductivity, forms good bond between the parts so that thermal loss is minimum.In addition, some application scenario (application scenario that for example has motion or vibrating mass) also requires substrate to have favorable mechanical stability.
US2008/0271771 relates to a kind of thermo-electric conversion module that comprises the substrate that thermal conductivity is good, and said substrate is made up of aluminum or aluminum alloy, and said aluminum or aluminum alloy has anode oxide film to guarantee electric insulation.Anodic oxidation is the oxidation reaction that takes place at anode in the electrolytic process, Al
2O
3Anode oxide film is formed on the aluminum or aluminum alloy surface through electrolysis aluminum or aluminum alloy in electrolyte solution (such as sulfuric acid).
Have been found that disclosed oxide-film can not prevent short circuit reliably in U.S.'s list of references.And for the high temperature application scenario as from waste gas, fusing bed, motor, reclaiming heat, heat source temperature maybe be up to 600 ℃, because 663 ℃ of the low melting points of aluminium, the aluminum supporter can not be used safely.
Summary of the invention
Target of the present invention provides a kind of electrothermal module that on substrate, has improved electrical insulating material.Preferably, substrate should have the thermal endurance higher than aluminium.
Embodiment
According to the present invention; This target realizes through following electrothermal module; Said module comprises one group of p type and the n N-type semiconductor N that is connected in series through conductive contact; Arrive the substrate of high thermal conductivity during wherein the conductive contact contact has, ohmmeter surface layer and the conductive contact electric insulation of said substrate through comprising ceramic material.
Conductive contact can for example be supported on substrate or the semiconductor/thermoelectric material.
Also through being used to prepare the method realization of above-mentioned electrothermal module, wherein said method comprises the step that adds the resistance superficial layer through electrophoretic deposition to undercoat to this target.
This target also through with above-mentioned electrothermal module as the weather control of heat pump, be used for taking one's seat furniture, vehicle and building, be used in refrigerator and (clothing) drying machine, be used for, realize as utilizing the generator (generator) of thermal source or being used for cooling electronic device at separating substances process heating and cooling simultaneously stream.
This target also heat pump, cooler, refrigerator, (clothing) drying machine, the generator that utilizes thermal source through comprising at least one above-mentioned electrothermal module, become the generator of electric energy to realize thermal power transfer.
According to the present invention, found that ceramic material forms good, firm thin electric insulation barrier layer under the situation that covers whole module surface on substrate.Electrothermal module according to the present invention has suitable strength characteristics, and is stable under the continuous operating temperature up to 600 ℃, and shows good thermal conductance and good resistive.
Preferably, the ohmmeter surface layer is formed by the coating of the mixture of ceramic material or glass and ceramic material.Ceramic material can be selected from various ceramic materials with good insulation properties.Preferably, ceramic material comprises alumina, zirconia or its mixture.Ceramic material can be used to form mixture with glass; Wherein the weight ratio of ceramic material is that 5-95% and weight of glass ratio are 95-5%; The weight ratio of preferably ceramic material is that 10%-90% and weight of glass ratio are 90-10%, and the weight ratio of ceramic material is that 20-80% and weight of glass ratio are 80-20% especially.In addition, preferably adopt pure ceramic material.
Substrate is preferably metal or metal alloy, semimetal, semiconductor, graphite, conductivity ceramics or its combination, is preferably metal or metal alloy.More preferably, substrate is heat-resisting steel, iron or nickel alloy.Preferred metal substrate comprises FeCr alloy, Crofer ferritic steel, nickel-plated steel and Ni Cr alloy, for example sells with
.Other metal substrate that preferably has the thermal stability higher than aluminum or aluminum alloy also is suitable for the present invention.
The geometry of substrate can be selected from any suitable intended shape that the application scenario needs.Not restriction of shape for substrate.Preferably, metal substrate is the planar metal substrate of similar paillon foil or sheet material or is formed by it through being shaped.
Can form such thermoelectric device, wherein substrate is formed directly into expectation and reclaims from it on the high temperature surface of main body of waste heat (for example from engine or blast pipe surface).For example, the metal liner egative film can form cylindrical so that insert or constitute the part of blast pipe.
Substrate can have 3 dimensional coil geometry arbitrarily, and it preferably can obtain through forming substrate slice.Therefore other dimension in thickness proportion such as sheet material, sheet material, cylinder, the circle etc. is little.
The thickness of the ohmmeter surface layer on the substrate is preferably between 1 μ m-500 μ m, more preferably between 1-100 μ m, especially between 15-35 μ m.
On the conductive contact of electrothermal module can deposit or be applied at the bottom of the electrically insulating substrate, perhaps they can deposit or be applied on the thermoelectric material.
Thermoelectric design according to the present invention allows electrode is integrated on the cated electric insulation metal substrate.Electrode can prepare through several kinds of deposition processs, for example photoetching, injection, spraying, printing, dipping.Specific resistive surface allows to have the electrode very uniformly of expectation thickness.Can obtain thickness according to the present invention be the high-quality electrode of 100nm-1mm.
In addition, according to the present invention, can thermoelectric material embedded, insert and put or insert in the solid matrix, wherein host material has low conduction and thermal conductivity, and is preferably the combination of pottery, glass, quartz, aeroge or these materials.Matrix protection heat and power system (material and contact) does not take place to degenerate and polluted because of the external factor as humidity, oxygen or chemical substance.
Matrix can insert and put or be inserted between the metal substrate of two isolation.Electrode can be applied on the substrate or thermoelectric material of isolation.Matrix is made up of thermal conductivity low material or material blends, so that heat passes through thermoelectric material, but does not pass through matrix.Although above-mentioned material is preferred, can adopt the non-conductive material of any lower thermal conductivity.
The ohmmeter surface layer can be applied on the substrate through any suitable method.Preferably, the ohmmeter surface layer is applied on the substrate through electrophoretic deposition.
Term " electrophoretic deposition (EPD) " comprises electropaining, electroplating cathode electro-deposition and electrophoretic coating or electrophoresis spraying in context of the present invention.The characteristics of this method are that the colloidal particles that is suspended in the liquid medium moves (electrophoresis) under electric field action, and are deposited on the electrode.Any can form ceramic coating or contain ceramic coating and can be used in form the stable suspersion thing and all can be used in the electrophoretic deposition with the colloidal particles that carries electric charge.This comprises such as pottery and this type of ceramic/glass mixture material.
This method can be used for material is applied on any conductive surface.In actual processing conditions and spendable device, the material that is deposited is that mainly determining cause is plain really.
Because the electrophoresis spraying process is widely used in numerous industries, moisture EPD is the most general EPD method of commercial use.Yet the application of non-water power swimming deposition also is known.The application of non-water EPD is used to make electronic unit and produces ceramic coating.The advantage of non-water method is that the gas of having avoided the electrolysis of water and having followed electrolysis to take place produces.
This method is used to apply coating to the metallic product in industry.It has been widely used in applying car body and parts, tractor and jumbo, electric switch gear, instrument, metal furniture, container for drink, securing member and a lot of other industrial products.
This method has the advantage that it is used widely:
1, the coating that applies of this method has coating layer thickness and imporosity very uniformly usually;
2, can apply the inner chamber and the outer surface of complicated structure object easily;
3, coating speed is higher relatively;
4, degree of purity is higher relatively;
5, be suitable for multiple material (for example pottery, glass etc.);
6, coating ingredients is easy to control;
7, normally automation of this method, comparing with other painting method needs less manpower;
8, the efficient utilization of coating material makes cost lower than other method;
9, with respect to the coating of their substituted solvent loads, the risk of normally used aqueous methods breaking out of fire is lower.
The whole industrial process of electrophoretic deposition comprises following subprocess:
1, needs to prepare the object that is coated to apply.This generally includes the certain cleaning process, and can comprise and apply conversion coating, normally applies the inorganic phosphate coating.
2, coating procedure itself generally includes parts is immersed container or the vessel that keep applying body lotion or coating solution, and utilizes electrode to apply direct current and bathe night through EPD.In electropaining or electrophoresis paint application, use the direct voltage of 25-400 volt usually.Applying object is one of electrode, and uses one group " to electrode " for forming the loop.
3, after deposition, the rinsing object is to remove the not body lotion of deposition usually.Rinse cycle can utilize ultrafilter so that dewater from the part of the body lotion that applies vessel, to be used as the rinsing material.If the use ultrafilter, then the material that gets off of all rinsings all can return the coating vessel, thereby realizes the high usage of coating material, and reduces the refuse quantity that enters environment.
4, after rinsing, cure usually or sintering process.This will make that coating (its may because the gas in the deposition process produces porous) becomes smooth and continuous.
There are two kinds of EPD methods, i.e. anode and cathode method.In anode process, the negative electrical charge material is deposited on positive charge electrode or the anode.In cathode method, the positive charge material is deposited on negative electrical charge electrode or the negative electrode.
When applying electric field, all charge specieses all move towards the electrode that has opposite charges through electrophoresis process.Exist several can make material be deposited on the mechanism on the electrode.
Institute's coating deposited has apparently higher than the resistance that is coated object.Along with the deposited film deposition, resistance increases.Therefore the increase of resistance is directly proportional with the thickness of deposited film, and under given voltage, electric current thickens along with film and diminishes, and slows down or stop to take place the point of (self restriction) until finally reaching deposition.Therefore, the voltage that applies is the major control to the film applied amount.
Application temperature also is the variable that influences the EPD process.Application temperature influences the conductivity of body lotion conductivity and deposited film, and it raises along with temperature and increases.Temperature also influences the viscosity of deposited film, and it influences the ability that deposited film discharges formed any bubble then.
In the deposition of ceramic material, avoid water generation electrolysis if desired, then should avoid in moisture EPD, applying the voltage that is higher than 3-4V.Yet also possibly apply higher voltage to obtain bigger coating layer thickness or to improve deposition velocity.In this application, utilize organic solvent to replace water as liquid medium.Employed organic solvent is polar solvent normally, such as pure and mild ketone.The examples of solvents that is suitable for being used in the electrophoretic deposition is ethanol, acetone and methyl ethyl ketone.
In electrophoresis according to the present invention, ceramic material preferably includes alumina, zirconia, titanium dioxide, silica, boron oxide or its mixture.Also other additive or element can be arranged, for example Ba, Sr, Na, Li, K, Pb, Ta, Hf, W, Mo, Cr, Ir, La, In, Ga, normally their oxide.
Alternatively, after electrophoretic deposition, carry out isostatic pressing, then sinter to, so that metallic plate has favorable mechanical stability and excellent electric insulating near solid density.
Preferably under 650-1400 ℃ temperature, under air or inert gas (especially nitrogen) environment, carry out sintering.
As for thermoelectric material, can use all thermoelectric materials according to the present invention.Typical thermoelectric material for example is US5,448,109, those disclosed among the WO 2007/104601, WO 2007/104603.Preferred lead telluride.
These materials reactivity of the mixture through discrete cell composition or its alloy usually grind or preferably generate through congruent melting and reaction.Generally speaking, have been found that reactive grind or to be at least 1 hour be favourable reaction time of preferred congruent melting.
Thermoelectric material generally prepares in the quartz ampoule of finding time and sealing.Mixing through the composition that uses rotatable and/or tiltable baking box to guarantee to be held.When reaction finishes, baking box is cooled off.From baking box, take out quartz ampoule then, and the semi-conducting material of bulk is thinly sliced.These thin slices are cut into the long small pieces of about 1-5mm then, and it can be used to make electrothermal module.
Except quartz ampoule, can also utilize the pipe or the bottle that present other material of inertia about semi-conducting material (for example tantalum).
Except pipe, can also use other vessel with suitable shape.Can also utilize other material (for example graphite) as the vessel material, prerequisite is that they present inertia about semi-conducting material.These materials can also be synthetic through the fusing/congruent melting process in the induction furnace (for example graphite ceramic or quartz crucible).
This has proposed to comprise the method for following method step:
(1) melts the mixture of discrete cell composition or its alloy and quaternary at least or ternary compound jointly;
(2) grind the material that in method step (1), obtains;
Moulded parts is suppressed or be squeezed into to the material that (3) will in method step (2), obtain, and
(4) alternatively, the moulded parts that in method step (3), obtains of sintering.
These semi-conducting materials can method known by one of skill in the art and that for example in WO98/44562, US 5,448,109, EP-A-1102334 or US 5,439,528, describe combine to form thermoelectric generator or Peltier structure.
Through changing the chemical composition of thermoelectric generator or Peltier structure, can provide different systems to satisfy the different demands in the possible in a large number application scenario.Therefore thermoelectric generator of the present invention or Peltier structure have widened the range of application of these systems.
The invention still further relates to the use of electrothermal module of the present invention:
As heat pump;
The weather control of furniture, vehicle and building is used to take one's seat;
Be used in refrigerator and (clothing) drying machine;
Be used at separating substances process heating and cooling simultaneously stream, said separation process such as:
-absorption;
-drying;
-crystallization;
-evaporation;
-distillation;
As utilizing the generator of thermal source, said thermal source such as:
-solar energy;
-underground heat;
The combustion heat of-fossil fuel;
Discarded thermal source in-vehicle and the fixed cell;
Fin in the evaporation of-liquid;
-biological thermal source;
Be used for the cooling electric parts;
As the generator that for example in motor vehicle, heating system or power station, thermal power transfer is become electric energy.
The invention still further relates to and comprise at least one heat pump, cooler, refrigerator, (clothing) drying machine, thermal power transfer is become the generator of electric energy or utilizes the generator of thermal source according to electrothermal module of the present invention.
Describe the present invention referring to following instance.
Instance
(a) ceramic coating
Dusty material is the aluminium oxide of partially stabilized zirconia of the yittrium oxide of MEL chemical industry and Sumitomo chemical company.It is the particle size distribution of 0.2 μ m that the suspended matter of these materials in amylalcohol grinds the formation average through vibrational energy.EPD carries out on the negative electrode that the metal foil substrate by the 60mm * 60mm that is supported around 4 edges constitutes, and makes that the deposition region is 44mm * 44mm.The deposition gesture is 30V.For avoiding dry and crack problems occurring, adopt three-step approach because of deposited film shrinks.
In each step, deposit about 2 minutes, will from body lotion, take out through the substrate that applies then and it will be carried out drying.Repeat this process, make total sedimentation time be about 6 minutes.
Through isostatic pressing the good coating of outward appearance is for further processing, then under all temps to its sintering 1 hour, make it near solid density.Measured value according to deposit weight and area is confirmed coating layer thickness, and the solid density of wherein supposing alumina is 3.965g/cm
3, zirconic solid density is 5.89g/cm
3Shown in table 1 and 2, zirconic coating layer thickness is about 20 μ m, and the coating layer thickness of alumina is about 30 μ m.
Be used to electro-deposition through the metallic plate that applies and electric insulation is handled.After covering coating,, coating applies platinum coating on the selected sample area through being brushed.Burnt the platinum coating 30 minutes with fire down at 800 ℃.Be designated as the resistance of the sample of X in the evaluation form 1 and 2.Insulation effect according to following content test coating:
Test block through applying is sandwiched between between two corrosion resistant plates that are electrically insulated from each other.Pressure on the nip region is 2N/mm
2Utilize external voltage source on two steel plates, to form the voltage of 15V, and measure electric current.The minimum detection limit value of electric current is 0.010mA.
Table 1
Zirconia coating
Table 2
The alumina coating
| No | Metal substrate | Coating layer thickness (μ m) | Sintering temperature ℃/environment | Ceramic coating resistance |
| 19 ＊ | The FeCr alloy | 28.0 | 1325 air | |
| 20 ＊ | Ferritic steel | 28.5 | 1300 nitrogen | Infinitely great |
| 21 | Nickel-plated steel | 26.6 | 1325 argon gas/hydrogen | |
| 22 | Inconel | 26.3 | 1325 argon gas/hydrogen | |
| 23 ＊ | The FeCr alloy | 28.7 | 1325 air |
| 24 | The FeCr alloy | 30.2 | 1325 air | Infinitely great |
| 25 | The FeCr alloy | 29.3 | 1325 air | Infinitely great |
| 26 | The FeCr alloy | 28.4 | 1325 air |
(b) glass-ceramic composite coating
Through with the glass grinding powdered, with Sumitomo alumina powder and be distributed to and produce the glass-ceramic composite powder suspended matter that is suitable for EPD in the alcohol.The glass that uses in this compound is aluminium borate glass, and its component is 46%SiO
2, 25%B
2O
3, 10%Al
2O
3, 4%Na
2O, 3%CaO, 6%SrO and 6%BaO.Make an experiment and on the FeCr Alloy Foil, form the composite coating of 80 weight % glass and 20 weight % alumina with the EPD that is about 1 minute through sedimentation time.Coating evenly, toughness, no texture and imporosity or minute crack.The thickness of glass/alumina coating is 7 μ m.Further EPD test shows can form thick glass coating to 30 μ m on the FeCr alloy, still the thermal conductivity owing to glass is low, therefore preferred shallow layer for thermoelectric applications.
Also can obtain to contain the coating of other glass/alumina ratio (from 100% glass to 100% alumina) by this method.Yet,, therefore in thermoelectric applications, do not expect high glass ratio because the thermal conductivity (1W/mK) of glass is lower than alumina (30W/mK).On the other hand, the higher compound of glass content is easier to handle, and this makes it possible to make thinner coating, does not exist simultaneously and pin hole or risk of short-circuits occur.The possible embodiment of this aspect of the present invention is shown in the table 3.
Table 3
Possible glass: alumina coating
| % glass | The % alumina | Thickness (μ m) |
| 0 | 100 | 30 |
| 20 | 80 | 20 |
| 40 | 60 | 10 |
| 80 | 20 | 5 |
(c) the FeCr alloy (comparison) of thermal oxidation
The FeCr alloy sample of uncoated (plate that paillon foil and 1mm are thick) in air ambient under 1100 ℃ temperature heat treated 2 hours, the α-Al that forms with the thermal oxidation that obtains because of alloy
2O
3Insulating barrier.The thickness of this layer is in the scope of 0.5-0.6 μ m.In the outstanding electric contact of the test wing (test wing), these surface oxide film have presented the evidence of electrical insulating property difference.
The FeCr alloy sample of uncoated (plate that paillon foil and 1mm are thick) in air-flow under 1100 ℃ temperature heat treated 2 hours.This heat treatment obtains the α-Al through the air-flow oxidation formation of alloy
2O
3Insulating barrier.The thickness of this layer is in the scope of 1.5-2 μ m.The resistance measurement test result shows that this coating does not obtain enough insulation (under 0.37mV, measuring the electric current of 2A).
Claims (14)
1. electrothermal module, it comprises one group of p and the n N-type semiconductor N that is connected in series through conductive contact, during said conductive contact contact has to the substrate of high thermal conductivity, ohmmeter surface layer and the conductive contact electric insulation of said substrate through comprising ceramic material.
2. electrothermal module as claimed in claim 1, wherein said ohmmeter surface layer is formed by the coating of the mixture of ceramic material or glass and ceramic material.
3. like each described electrothermal module in claim 1 or 2, wherein said substrate is metal, metal alloy, semimetal, semiconductor, graphite, conductivity ceramics or its combination.
4. like each described electrothermal module among the claim 1-3, the thickness of wherein said ohmmeter surface layer is between 1 μ m-500 μ m, preferably between 1 μ m-100 μ m.
5. like each described electrothermal module among the claim 1-4, on wherein said conductive contact is deposited at the bottom of the electrically insulating substrate.
6. like each described electrothermal module among the claim 1-4, wherein said conductive contact is applied on the thermoelectric material.
7. like each described electrothermal module among the claim 1-6; Wherein said thermoelectric material is embedded into, inserts and puts or inserts in the solid matrix; Wherein said host material has low conductivity and thermal conductivity, and is preferably the combination of pottery, glass, mica, aeroge or these materials.
8. like each described electrothermal module among the claim 1-7, wherein said ohmmeter surface layer is applied on the substrate through electrophoretic deposition.
9. like each described electrothermal module among the claim 1-8, wherein said substrate is heat-resisting steel, iron or nickel alloy.
10. like each described electrothermal module among the claim 1-9, wherein said ceramic material comprises alumina, zirconia, titanium dioxide, silica, boron oxide or its mixture.
11. like each described electrothermal module among the claim 1-10, wherein said substrate has unrestricted 3 dimensional coil geometry, said shape preferably can obtain through forming substrate sheet.
12. one kind is used for preparing the method like each described thermoelectric material of claim 1-11, it comprises the step that applies said ohmmeter surface layer through electrophoretic deposition to said substrate.
13. according to the purposes of each described electrothermal module among the claim 1-11, said purposes for as the weather control of heat pump, be used for taking one's seat furniture, vehicle and building, be used in refrigerator and (clothing) drying machine, be used at separating substances process heating and cooling simultaneously stream, as utilizing the generator of thermal source or being used for cooling electronic components.
14. a heat pump, cooler, refrigerator, (clothing) drying machine, utilize thermal source generator, be used for thermal power transfer is become the generator of electric energy, it comprises that at least one is like each described electrothermal module among the claim 1-11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09157158.8 | 2009-04-02 | ||
| EP09157158 | 2009-04-02 | ||
| PCT/EP2010/054268 WO2010115792A1 (en) | 2009-04-02 | 2010-03-31 | Thermoelectric module with insulated substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102449791A true CN102449791A (en) | 2012-05-09 |
Family
ID=42357317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800237638A Pending CN102449791A (en) | 2009-04-02 | 2010-03-31 | Thermoelectric module with insulated substrate |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20120017963A1 (en) |
| EP (1) | EP2415090B1 (en) |
| JP (1) | JP2012523111A (en) |
| KR (1) | KR20120007027A (en) |
| CN (1) | CN102449791A (en) |
| CA (1) | CA2757530A1 (en) |
| RU (1) | RU2011144115A (en) |
| SG (1) | SG174559A1 (en) |
| TW (1) | TW201042788A (en) |
| WO (1) | WO2010115792A1 (en) |
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| CN107124108A (en) * | 2016-02-25 | 2017-09-01 | 西门子公司 | Thermal management method, device and the equipment for including high-power heater element |
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| EP2411324A2 (en) * | 2009-03-24 | 2012-02-01 | Basf Se | Self-organising thermoelectric materials |
| US9082928B2 (en) | 2010-12-09 | 2015-07-14 | Brian Isaac Ashkenazi | Next generation thermoelectric device designs and methods of using same |
| JP2013026334A (en) * | 2011-07-19 | 2013-02-04 | National Institute Of Advanced Industrial & Technology | Stacked thermoelectric conversion module |
| US10454013B2 (en) * | 2012-11-16 | 2019-10-22 | Micropower Global Limited | Thermoelectric device |
| US9276190B2 (en) | 2013-10-01 | 2016-03-01 | The Pen | Practical method of producing an aerogel composite continuous thin film thermoelectric semiconductor material by modified MOCVD |
| US9040339B2 (en) | 2013-10-01 | 2015-05-26 | The Pen | Practical method of producing an aerogel composite continuous thin film thermoelectric semiconductor material |
| CN105207529A (en) * | 2015-10-28 | 2015-12-30 | 蒋安为 | Infrared light power generation device |
| NO341705B1 (en) * | 2016-02-22 | 2018-01-02 | Tegma As | Thermoelectric half-cell and method of production |
| KR102050138B1 (en) * | 2017-12-07 | 2019-11-28 | 한국세라믹기술원 | Multilayered substrate of electrode layer/insulation layer, manufacturing method thereof,and thermoelectric generator module comprising the same |
| DE102019207227B4 (en) * | 2019-05-17 | 2021-10-07 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the production of thermoelectric elements with electrical connection contacts as well as a thermoelectric module produced with the process |
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- 2010-03-31 RU RU2011144115/28A patent/RU2011144115A/en not_active Application Discontinuation
- 2010-03-31 EP EP10711894.5A patent/EP2415090B1/en not_active Not-in-force
- 2010-03-31 CN CN2010800237638A patent/CN102449791A/en active Pending
- 2010-03-31 WO PCT/EP2010/054268 patent/WO2010115792A1/en active Application Filing
- 2010-03-31 SG SG2011069424A patent/SG174559A1/en unknown
- 2010-03-31 KR KR1020117026168A patent/KR20120007027A/en not_active Application Discontinuation
- 2010-03-31 US US13/259,872 patent/US20120017963A1/en not_active Abandoned
- 2010-03-31 JP JP2012502658A patent/JP2012523111A/en active Pending
- 2010-04-02 TW TW099110431A patent/TW201042788A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201042788A (en) | 2010-12-01 |
| CA2757530A1 (en) | 2010-10-14 |
| KR20120007027A (en) | 2012-01-19 |
| EP2415090A1 (en) | 2012-02-08 |
| JP2012523111A (en) | 2012-09-27 |
| RU2011144115A (en) | 2013-05-10 |
| SG174559A1 (en) | 2011-10-28 |
| EP2415090B1 (en) | 2013-10-23 |
| US20120017963A1 (en) | 2012-01-26 |
| WO2010115792A1 (en) | 2010-10-14 |
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